CN110021742A - A kind of nickle cobalt lithium manganate composite material and preparation method - Google Patents
A kind of nickle cobalt lithium manganate composite material and preparation method Download PDFInfo
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- CN110021742A CN110021742A CN201910255242.8A CN201910255242A CN110021742A CN 110021742 A CN110021742 A CN 110021742A CN 201910255242 A CN201910255242 A CN 201910255242A CN 110021742 A CN110021742 A CN 110021742A
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- lithium manganate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
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Abstract
The present invention provides a kind of nickle cobalt lithium manganate composite materials, it includes 811 nickel-cobalt lithium manganate materials and polyurethane material, polyurethane material is wrapped in the surface of 811 nickel-cobalt lithium manganate materials, and the quality of polyurethane material is the 0.18-4.5% of the quality of 811 nickel-cobalt lithium manganate materials.The present invention also provides a kind of preparation methods of nickle cobalt lithium manganate composite material.The present invention can improve the hygroscopic problem of nickle cobalt lithium manganate compared to the prior art, and the problem of be easily achieved scale industrial production, can solve battery difficult processing.
Description
Technical field
The present invention relates to field of lithium ion battery, in particular to a kind of nickle cobalt lithium manganate composite material and its preparation
Method.
Background technique
As the lithium ion battery material of most mainstream at present, ternary material is considered as following development trend, with new
The requirement of the continuous development in energy automobile market, cruising ability and specific energy for battery is continuously improved, nickelic ternary material
Also in the ratio that nickel is continuously improved in material.
Meanwhile the requirement with ternary lithium battery new-energy automobile policy for energy density, ternary lithium battery will be cities
The inevitable choice of field, and monomer energy density 350wh/kg are realized 2020,811 system of ternary be just particularly important；Separately
Outside, for cobalt as scarce resource, the ratio of required cobalt is relatively fewer in ternary 811, smaller by cobalt valence influence of fluctuations.
However, NCM811 material the problem of there is hygroscopic, battery difficult processings, thus constrain NCM811 material and possess
High-energy density, while making NCM811 material that there is some potential safety problems.
Summary of the invention
In consideration of it, the present invention provides a kind of nickle cobalt lithium manganate composite material and preparation methods, it is intended to solve existing
The problem of hygroscopic present in nickel-cobalt lithium manganate material, battery difficult processing.
Thus, on the one hand, the present invention provides a kind of nickle cobalt lithium manganate composite materials comprising 811 nickle cobalt lithium manganate materials
Material and polyurethane material, polyurethane material are wrapped in the surface of 811 nickel-cobalt lithium manganate materials, and the quality of polyurethane material is 811
The 0.18-4.5% of the quality of nickel-cobalt lithium manganate material.
Further, the quality of above-mentioned polyurethane material is the 0.8-3.5% of the quality of nickle cobalt lithium manganate.
Further, in above-mentioned 811 nickel-cobalt lithium manganate material, lithium source is lithium carbonate, and nickel source is nickelous carbonate, and manganese source is nitric acid
Manganese, cobalt source are cobaltosic oxide.
On the other hand, the present invention provides a kind of preparation methods of nickle cobalt lithium manganate composite material comprising following preparation
Step: 811 nickel-cobalt lithium manganate materials are at the uniform velocity stirred in the solution of dissolution polyurethane material, the quality of polyurethane material is
The 0.18-4.5% of the quality of 811 nickel-cobalt lithium manganate materials is calcined, a kind of obtained nickle cobalt lithium manganate composite wood after dry
Material.
Further, 1-8h is calcined under conditions of nitrogen environment and 200-450 DEG C after drying, a kind of obtained nickel cobalt manganese
Sour lithium composite material.
Further, the quality of above-mentioned polyurethane material is the 0.8-3.5% of the quality of nickle cobalt lithium manganate.
Further, comprising the following steps:
1) by lithium source, nickel source, manganese source and cobalt source according to Li (Ni0.8Co0.1Mn0.1)O2The stoichiometric ratio of middle each element claims
Amount after ball milling 2.5-4.5h, 1-6h is calcined under conditions of pure oxygen environment and 400-550 DEG C, is obtained after cooling compound in ethanol
Object；
2) by compound in pure water after ball milling 1.5-4.5h, expansion drying under the conditions of 100-250 DEG C of temperature, then
1-8h is calcined under conditions of pure oxygen environment and 500-700 DEG C, finally obtains 811 nickel-cobalt lithium manganate materials.
Further, above-mentioned steps 1) in, compound is obtained by misting cooling.
A kind of nickle cobalt lithium manganate composite material and preparation method provided by the present invention, since polyurethane material is wrapped in
811 nickle cobalt lithium manganate surfaces, polyurethane material can separate nickle cobalt lithium manganate and the external world, therefore relative to traditional nickel
Cobalt lithium manganate material, this nickle cobalt lithium manganate composite material can improve the hygroscopic problem of nickle cobalt lithium manganate；In addition, entire nickel
The preparation process of cobalt manganic acid lithium Li composite material is easy to operate, it is easy to accomplish scale industrial production can solve battery
The problem of difficult processing.
Detailed description of the invention
By reading the following detailed description of the preferred embodiment, various other advantages and benefits are common for this field
Technical staff will become clear.The drawings are only for the purpose of illustrating a preferred embodiment, and is not considered as to the present invention
Limitation.And throughout the drawings, the same reference numbers will be used to refer to the same parts.In the accompanying drawings:
Fig. 1 is a kind of preparation flow figure of nickle cobalt lithium manganate composite material provided in an embodiment of the present invention；
Fig. 2 is modification front and back XRD and the pattern comparison of a kind of nickle cobalt lithium manganate composite material provided in an embodiment of the present invention
Figure；
Fig. 3 is modification front and back and water and the electrolyte of a kind of nickle cobalt lithium manganate composite material provided in an embodiment of the present invention
Compatibility comparison diagram；
Fig. 4 is that high temperature, the room temperature before and after a kind of modification of nickle cobalt lithium manganate composite material provided in an embodiment of the present invention follow
Ring comparison diagram；
Fig. 5 is a kind of 0.2C discharge curve of nickle cobalt lithium manganate composite material provided in an embodiment of the present invention.
Specific embodiment
Exemplary embodiments of the present disclosure are described in more detail below with reference to accompanying drawings.Although showing the disclosure in attached drawing
Exemplary embodiment, it being understood, however, that may be realized in various forms the disclosure without should be by embodiments set forth here
It is limited.On the contrary, these embodiments are provided to facilitate a more thoroughly understanding of the present invention, and can be by the scope of the present disclosure
It is fully disclosed to those skilled in the art.
Instrument used in following embodiment includes:
Sand mill, model CMSD2000, manufacturer are Shanghai Yi Ken mechanical equipment Co., Ltd；
Rotatingandflashstreamingdrier, model XSG, manufacturer are Changzhou and positive drying equipment Co., Ltd；
Tubular type batch-type furnace, model JD-10-12TC, manufacturer are Suzhou east of a river precision instrument Co., Ltd；
Air batch-type furnace, model NA 250/45, manufacturer are Conrad Naber company.
Embodiment one:
As shown in connection with fig. 1, by 26.85g lithium carbonate, 64.07g nickelous carbonate, 7.8g manganese nitrate, 8.2g cobaltosic oxide is mixed
500mL ethyl alcohol is added after conjunction in Ball-stirring mill, stirs 2.5h；It is dry that obtained mixed slurry is carried out to flash distillation in air dry oven
It is dry, it is then once calcined in oxygen, a calcination temperature is 400 DEG C, time 4.5h, and it is compound to obtain forerunner after cooling
Body；
By obtained forerunner's complex, secondary ball milling carries out treatment with micron, Ball-milling Time 3.5h in high speed sand mill；
Slurry after sand milling is subjected to expansion drying, the temperature of expansion drying is 120 DEG C；Secondary clacining, temperature are carried out in oxygen again
It is 700 DEG C, time 7h, obtains nickel-cobalt lithium manganate material Li (Ni0.8Co0.1Mn0.1) 02.
811 obtained nickel-cobalt lithium manganate materials are stirred in the acetone soln of dissolution polyurethane material, obtained mixing
Liquid is dried in air dry oven；It is calcined three times in nitrogen after drying, temperature is 400 DEG C, and time 4h is obtained
02 composite material of nickle cobalt lithium manganate Li (Ni0.8Co0.1Mn0.1).
Embodiment two:
Other are identical as content described in embodiment one, the difference is that, the ball milling 4.5h in Ball-stirring mill, primary calcining temperature
Degree is 550 DEG C, time 1h；The secondary ball milling time is 1.5h；The temperature of expansion drying is 250 DEG C；The temperature of secondary clacining is
500 DEG C, time 3h；
Obtained nickel-cobalt lithium manganate material is stirred in the acetone soln of dissolution polyurethane material, obtained mixed liquor exists
It is dried in air dry oven.It is calcined three times in nitrogen after drying, temperature is 450 DEG C, and time 6h obtains nickel cobalt
02 composite material of LiMn2O4 Li (Ni0.8Co0.1Mn0.1).
Obviously change as shown in Fig. 2, obtained nickle cobalt lithium manganate composite material has on the XRD and pattern after modification
It is kind.
As shown in figure 3, obtained nickle cobalt lithium manganate composite material after modification with have in the compatibility of water and electrolyte
It is obviously improved.
As shown in figure 4, obtained nickle cobalt lithium manganate composite material is clearly more stable on the capacity after modification；Such as figure
Shown in 5,02 composite material of obtained Li (Ni0.8Co0.1Mn0.1) is subjected to 0.2C charge and discharge, capacity is up to 200mAh/g.
Therefore, a kind of nickle cobalt lithium manganate composite material and preparation method provided by the present embodiment, due to polyurethane material
Material is wrapped in 811 nickle cobalt lithium manganate surfaces, and polyurethane material can separate nickle cobalt lithium manganate and the external world, therefore relative to
Traditional nickel-cobalt lithium manganate material, this nickle cobalt lithium manganate composite material can improve the hygroscopic problem of nickle cobalt lithium manganate；This
Outside, the preparation process of entire nickle cobalt lithium manganate Li composite material is easy to operate, it is easy to accomplish scale industrial production, it can be with
Solve the problems, such as battery difficult processing.
Obviously, various changes and modifications can be made to the invention without departing from essence of the invention by those skilled in the art
Mind and range.In this way, if these modifications and changes of the present invention belongs to the range of the claims in the present invention and its equivalent technologies
Within, then the present invention is also intended to include these modifications and variations.
Claims (8)
1. a kind of nickle cobalt lithium manganate composite material, which is characterized in that including 811 nickel-cobalt lithium manganate materials and polyurethane material, institute
The surface that polyurethane material is wrapped in 811 nickel-cobalt lithium manganate material is stated, the quality of the polyurethane material is 811 nickel
The 0.18-4.5% of the quality of cobalt lithium manganate material.
2. a kind of nickle cobalt lithium manganate composite material according to claim 1, which is characterized in that the matter of the polyurethane material
Amount is the 0.8-3.5% of the quality of the nickle cobalt lithium manganate.
3. a kind of nickle cobalt lithium manganate composite material according to claim 1, which is characterized in that 811 nickle cobalt lithium manganate
In material, lithium source is lithium carbonate, and nickel source is nickelous carbonate, and manganese source is manganese nitrate, and cobalt source is cobaltosic oxide.
4. a kind of preparation method of nickle cobalt lithium manganate composite material, which is characterized in that including following preparation step: by 811 nickel cobalts
Lithium manganate material at the uniform velocity stirs in the solution of dissolution polyurethane material, and the quality of the polyurethane material is 811 nickel cobalt
The 0.18-4.5% of the quality of lithium manganate material is calcined after dry, obtains a kind of nickle cobalt lithium manganate composite material.
5. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 4, which is characterized in that after dry
1-8h is calcined under conditions of nitrogen environment and 200-450 DEG C, obtains a kind of nickle cobalt lithium manganate composite material.
6. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 4, which is characterized in that the poly- ammonia
The quality of ester material is the 0.8-3.5% of the quality of the nickle cobalt lithium manganate.
7. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 4, which is characterized in that including following
Step:
1) by lithium source, nickel source, manganese source and cobalt source according to Li (Ni0.8Co0.1Mn0.1)O2The stoichiometric ratio of middle each element is weighed in second
In alcohol after ball milling 2.5-4.5h, 1-6h is calcined under conditions of pure oxygen environment and 400-550 DEG C, obtains compound after cooling；
2) by the compound in pure water after ball milling 1.5-4.5h, expansion drying under the conditions of 100-250 DEG C of temperature, then
1-8h is calcined under conditions of pure oxygen environment and 500-700 DEG C, finally obtains 811 nickel-cobalt lithium manganate material.
8. a kind of preparation method of nickle cobalt lithium manganate composite material according to claim 7, which is characterized in that the step
1) in, the compound is obtained by misting cooling.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112864369A (en) * | 2021-03-19 | 2021-05-28 | 合肥国轩高科动力能源有限公司 | Modified high-nickel ternary cathode material and preparation method thereof |
| WO2022188635A1 (en) * | 2021-03-12 | 2022-09-15 | 合肥国轩高科动力能源有限公司 | Method for preparing coating-modified high-nickel ternary positive electrode material, and prepared material |
| CN115594234A (en) * | 2022-11-09 | 2023-01-13 | 合肥国轩高科动力能源有限公司（Cn） | m-LNCM712 cathode material, preparation method thereof and lithium ion battery |
| US11785798B2 (en) | 2020-10-27 | 2023-10-10 | Samsung Display Co., Ltd. | Display with dam surrounding opening |
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| CN107611424A (en) * | 2017-08-31 | 2018-01-19 | 龙能科技如皋市有限公司 | A kind of nickle cobalt lithium manganate composite wood and preparation method thereof |
| CN109088066A (en) * | 2018-09-26 | 2018-12-25 | 龙能科技如皋市有限公司 | A kind of nickle cobalt lithium manganate composite material and preparation method |
-
2019
- 2019-03-30 CN CN201910255242.8A patent/CN110021742A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107611424A (en) * | 2017-08-31 | 2018-01-19 | 龙能科技如皋市有限公司 | A kind of nickle cobalt lithium manganate composite wood and preparation method thereof |
| CN109088066A (en) * | 2018-09-26 | 2018-12-25 | 龙能科技如皋市有限公司 | A kind of nickle cobalt lithium manganate composite material and preparation method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11785798B2 (en) | 2020-10-27 | 2023-10-10 | Samsung Display Co., Ltd. | Display with dam surrounding opening |
| WO2022188635A1 (en) * | 2021-03-12 | 2022-09-15 | 合肥国轩高科动力能源有限公司 | Method for preparing coating-modified high-nickel ternary positive electrode material, and prepared material |
| CN112864369A (en) * | 2021-03-19 | 2021-05-28 | 合肥国轩高科动力能源有限公司 | Modified high-nickel ternary cathode material and preparation method thereof |
| CN112864369B (en) * | 2021-03-19 | 2022-02-18 | 合肥国轩高科动力能源有限公司 | Modified high-nickel ternary cathode material and preparation method thereof |
| CN115594234A (en) * | 2022-11-09 | 2023-01-13 | 合肥国轩高科动力能源有限公司（Cn） | m-LNCM712 cathode material, preparation method thereof and lithium ion battery |
| CN115594234B (en) * | 2022-11-09 | 2024-01-19 | 合肥国轩高科动力能源有限公司 | m-LNCM712 positive electrode material, preparation method thereof and lithium ion battery |
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Application publication date: 20190716 |